SK5352000A3 - ACID CLEANING COMPOSITIONS CONTAINING ALKOXYLATED AMINES ANDì (54) THEIR USE - Google Patents

Abstract

Use of 0.01-15 wt.% of an alkoxylated aliphatic amine with 8-20 carbon atoms and 1-8 units of alkoxylation improves the antimicrobial effectiveness of an acidic, antimicrobial composition comprising 0.01-15 wt.% of sulphamic acid. The invention also provides acidic, antimicrobial composition comprising: 0.01-15 wt.% of an alkoxylated aliphatic amine with 8-20 carbon atoms and 1-8 units of ethoxylation, 0.01-15 wt.% of a sulphamic acid, and a source of peroxygen species and a method of disinfecting surfaces which comprises the step of treating the surface with an acidic, antimicrobial composition of that type. Typically, the alkoxylated aliphatic amine is an ethoxylated tertiary amine of the general formula: H(A)x-N(R)-(A)yH wherein R is an alkyl or alkenyl group comprising 8-20 carbon atoms, A is an ethoxy group and x and y may be the same or different and are integers from 1-4. Preferably x and y are both 1 or 2. In preferred embodiments of the invention R is C14-C18 alkyl and is most preferably derived from oleic, palmitic or myristic acid.

Description

Technical field

The present invention relates to a process for the production of acidic cleaning compositions, in particular acidic antimicrobial cleaning compositions suitable for cleaning hard surfaces.

BACKGROUND OF THE INVENTION

Numerous processes for the production of stone removal preparations have been reported in the literature. These formulations generally contain a sufficient amount of acid, have a low pH and may contain a thickening agent so that the formulation can be retained and kept on inclined surfaces, such as inside toilet bowls. As will be discussed below, known thickeners include both ethoxylated and non-ethoxylated tertiary amines, either alone or in combination with a hydrotropic agent. Known acids for use in such formulations are amidosulfonic acid and phosphoric acid.

These preparations should preferably have antimicrobial effects and act against a wide variety of microorganisms. In order to achieve these effects, various bactericidal substances have been proposed as additives to these preparations.

GB 1443244 relates to acidic and stone removal compositions containing an ethoxylated tertiary amine, such as ETHOMEN S12 (N, N -dihydroxyethyloleylamine) as a thickening agent. The formulations also contain acids from the group of mineral acids and salts of strong inorganic acids such as amidosulfonic acid. Bactericidal agents are optionally useful.

FR 2459830 discloses compositions comprising unethoxylated and ethoxylated amines together with amidosulfonic acid. The composition may also contain disinfectants.

WO 95/27768 discloses cleaning compositions intended in particular for painted and plastic surfaces, comprising ethoxylated C10 to C18 aliphatic amines having 3 to 8 ethoxy units (preferably 4 to 6) and C6 to C10 carboxylic acids and / or organic or inorganic chelating agents. The preparations do not have disinfectant properties.

AU-A-57022/86 relates to cleaning systems comprising a mixture of amidosulfonic acid and phosphoric acid and an acid-resistant surfactant. Bactericidal agents are optionally useful and formalin is described as a bactericidal agent that improves the antibacterial effect of acids.

EP-B-0276501 discloses a thickened aqueous cleaning composition comprising 0.1 to 50 wt. % weak acid with pK > 2 (amidosulfonic acid is exemplified), 0.1 to 20 wt. % of amine, which may contain 2% oleyl-bis (2-hydroxyethyl) amine and 0.01% to 5% by weight of amine; hydrotroping agent (sodium oxylene sulfonate is exemplified). Disinfectants are optionally useful.

EP-A-0314232 relates to compositions which increase the viscosity at dilution and discloses that thickened liquid cleaning compositions can be prepared with an amine oxide, an amine (such as ETHOMEEN S12 ™), a betaine, a quaternary ammonium compound, and a hydrotropic agent. with an agent (sodium oxylenesulfonate). It is noted in the characteristic that amine oxides and quaternary ammonium compounds are known for their biocidal properties and that other microbiocides, including organic peroxyacids, can optionally be used. These preparations may have an acid, neutral or alkaline pH.

Accordingly, while certain thickening surfactants such as quaternary ammonium compounds and amine oxides are known for their antibacterial properties, it has been commonly proposed to add additional antimicrobial components to stone removal compositions where, in addition to the stone removal effects, antimicrobial properties.

It has now been found that formulations containing alkoxylated aliphatic amines as well as amidosulfonic acid have superior antimicrobial effects. This is probably due to the synergistic interaction of these components and this result is

-3 reaches regardless of the presence of other antimicrobial components, i. even in their absence.

It has now also been found that excellent stone removal and disinfectant effects have been achieved with formulations containing: a) an alkoxylated aliphatic amine, b)

I amidosulfonic acid, c) source of peroxygen species.

SUMMARY OF THE INVENTION

The invention is based on the use of 0.01 to 15 wt. of an alkoxylated aliphatic amine having an aliphatic hydrocarbon group of 8 to 20 carbon atoms and 1 to 8 units of alkoxylation per mole of amine to improve the antimicrobial effects of an acidic antimicrobial composition containing 0.01 to 15 wt. amidosulfonic acid and optionally a source of peroxygen.

In another embodiment, the invention provides an acidic microbial composition comprising: a) 0.01 to 15 wt. % of an alkoxylated aliphatic amine having 8 to 20 carbon atoms and 1 to 8 alkoxylation units; and c) optionally a source of peroxygen.

The invention further provides a method of disinfecting surfaces comprising treating a surface with an acidic antimicrobial composition comprising:

a) 0.01 to 15 wt. an alkoxylated aliphatic amine of 8 to 20 carbon atoms and 1 to 8 alkoxylation units,

b) 0.01 to 15 wt. of amidosulfonic acid.

amines

Alkoxylated aliphatic amine is a tertiary amine of the general formula:

H (A) _X -N (R) - (A) _Y H where R represents an alkyl or alkenyl group having 8 to 20 carbon atoms, A is ethoxy or propoxy and x and y may be the same or different and represent an integer from 1 to 4. R preferably has 8 to 18, most preferably 10 to 18 carbon atoms; x and y are preferably 1 to 3, most preferably 1 or 2. Preferred materials are

-4-ethoxylated amines wherein A is -OCH ₂ CH ₂ -. In other preferred embodiments of the invention, R is C 14 to C 18 alkyl or alkenyl and is, for example, derived from oleic, palmitic or myristic acid.

Preferred ethoxylated amines are, for example:

- N, N '- di (hydroxyethyl) oleylamine, which is available from AKZO under the trademark ETHOMEEN S12;

C12 to C18 aliphatic aminoethoxylates containing 2 or 3 ethoxy groups wherein from 20 to 40% of the aliphatic groups are unsaturated (i.e., R = C12 to C18 20 to 40% unsaturated, x = 1 and y = 1 or 2). An example of such a material is ETHOMEEN BTB / 12 ™, which is also available from AKZO and is a 65:35 mixture of N, N -di (hydroxyethyl) aliphatic amine derived from a fully hardened tallow and an oleyl derivative. Such a mixed material can be prepared by synthesis using primary materials such as ETHOMEEN HT ™ and ETHOMEEN S ™ in the desired ratio.

C12 to C16 alkyl amines containing 2 or (even more preferably) 3 ethoxy groups (i.e., R = C12 to C16 alkyl, x = 1 and y = 1 or more preferably 2).

As follows, the most suitable ethoxylated amines or mixtures of these amines are those where the aliphatic group is predominantly (more than 50%) derived from C16 and C18 fatty acids, where (on average) x + y is 2-3.

The preferred proportion of alkoxylated aliphatic amines is 1 to 10 wt. % of the product, most preferably 2 to 6 wt. product.

acids

A typical proportion of amidosulfonic acid is 1 to 10 wt. % of the product, preferably 2 to 6 wt. product.

Peroxygen sources

Typical sources of peroxygen are hydrogen peroxide, peracetic acid and / or other organic or inorganic sources. Hydrogen peroxide is the most preferred source

-5peroxygénu. A typical proportion of hydrogen peroxide is 1 to 10 wt. % of the product, preferably up to 8 wt. product.

Surfactants

The compositions of the present invention preferably comprise a nonionic surfactant and / or a hydrotropic agent.

Suitable nonionic detergent active compounds (surfactants) can generally be described as being formed by the condensation of alkylene oxide groups, which are naturally hydrophilic, with an organic hydrophobic compound, which may be naturally aliphatic or alkyl aromatic. The length of the hydrophilic polyoxylalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to provide a water-soluble compound with the desired degree of equilibrium between hydrophilic and hydrophobic elements. Preferred nonionic surfactants are alkoxylated alcohols and alkylphenols, most preferably ethoxylated alcohols.

Preferred ethoxylated alcohols have the general formula:

R ¹ - (OCH ₂ CH ₂ ) _m -OH wherein R ¹ is straight or branched C 8 to C 18 alkyl or hydroxyalkyl (preferably alkyl) and _m is an average of 1 to 14. Ethoxylated alcohols suitable for use in the present invention include the LIAL series available on the market from DAC, e.g., LIAL

111.10OEO [TM]. A typical proportion of nonionic surfactant in the product of the present invention is 0 to 5 wt.

Suitable hydrotropic substances are lower aliphatic alcohols, in particular ethanol, urea and / or alkaryl sulfonates, as well as salts, in particular alkali metal salts of toluene, cumene or xylene sulfonate.

Preferred hydrotropes are alkaryl sulfonates, most preferably sodium cumene sulfonate. A suitable material is ELTESOL SC 40 (TM Albright a

Wilson). A typical proportion of hydrotrope is from 0.05 to 2% by weight.

product.

In preferred embodiments of the invention, the alkoxylated aliphatic amine is present together with the anionic surfactant in a proportion of these materials so as to interact to achieve a thickening of the formulation.

Formulations containing alkaryl sulfonates are prepared so that their pH is less than 2, preferably less than 1.5, most preferably less than 1. Without being limited by theory, it is believed that at such a low pH, the ethoxylated amine behaves as a cationic surface. The active substance is reacted with an alkaryl sulfonate to form a water-insoluble gel which is deposited as a single layer on surfaces. It is believed that this single layer reduces the surface energy of the surface and limits or protects against scale deposition.

The preferred molar ratio of ethoxylated amine to anionic surfactant is 3 to 3.5, most preferably 3.25 to 3.5.

The preferred viscosity of the cleaning compositions of the present invention is 50 mPas to 1000 mPas at 11.7 fps and at 25 ° C using a Haake RV2 rotoviscometer ™ and MV bob.

The composition of the present invention preferably comprises:

a) 1 to 10 wt.%, most preferably 3 to 5 wt. amidosulfonic acid,

b) 1 to 10 wt.%, most preferably 2 to 5 wt. ethoxylated amine,

c) 0 to 5 wt.%, most preferably 0.05 to 1 wt. a nonionic surfactant,

d) 0.05 to 2 wt.%, most preferably 0.4 to 1.1 wt. anionic surfactant hydrotropic,

e) 1 to 10 wt.%, most preferably 4 to 6 wt. hydrogen peroxide.

Secondary components

In addition to the combination of thickening surfactants in the compositions of the invention, other thickeners may be added. Suitable thickeners are resins, especially xanthan gums. Preferred xanthan gums are the Kelzan (RTM) series (available from Kelco Corp.). If xanthan gums are present, their typical proportion is 0.05 to 1 wt%. The resulting viscosity of the formulation

Measured on a Haake RV2 rotoviscometer (RTM) is preferably from 10 to 200 mPas at 20 frames / sec. and at 25 ° C using MV1 bob. More preferred is a viscosity of 10 to 100 mPas under the above conditions.

Metal ion sequestering agents such as ethylenediaminetetraacetate, amino polyphosphonates (e.g., in the DEQUEST ™ range from Monsato) and phosphates and a wide variety of other polyfunctional organic acids and salts may also be optionally useful. Preferred metal ionic complexing agents are selected from dipicolinic acid, ethylenediaminetetraacetic acid (EDTA) and salts thereof, hydroxyethylidene diphosphonic acid (Dequest 2010), ethylenediaminetetra (methylenephosphonic acid) (Dequest 2040), diethylenetriamine (diethylenetriamine) (pentaethylenetriamine).

Optionally, components commonly found in detergent compositions, such as opacifiers, colorants, flavorings, and fluorescent substances, may also be included as co-components.

The preferred proportion of flavoring agents is 0.05 to 2 wt. Acid-stable aromatic agents are available from many sources.

The most preferred composition of the present invention consists of:

ETHOMEEN BTB / 12 by AKZO 2 to 5% ethoxylated amine amidosulfonic acid 4% hydrogen peroxide 5% LIAL 111.1OEO from DAC 0.1% non-ionic surface active substance ELTESOL SC40 from Albright 0.4 to 1.1% * nátriumkuménsulfonát BRILLIANT BLUE 9 from WJE 0.0021% Cl 307047 / color PERFUME by IFF 0,12% Othello 39 DEQUEST 2066 from Monsato 0 to 0.3 Water up to 100%

‘Variable adapts to viscosity

Typical products of said composition prepared with 3.0 wt. % of an amine and about 0.56 wt. SCSs are transparent, with a specific gravity of 1040 g / ml, an initial viscosity of 120 mPas at 106 sec- ¹ (at 25 ° C), an initial viscosity of 300 mPas at 11.7 sec- ¹ (at 25 ° C), and a pH of 0.9 (at 25 ° C).

In order that this invention may be more fully understood, the following non-limiting Examples are set forth below.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Antibacterial synergy

Enterococcus faecium Proeteus mirablis

Suspension tests were performed on the formulations of the invention and comparative formulations at typical dilutions used (2%) of the present invention. The following bacterial strains were used in suspension tests:

Pseudomonas aeruginosa ATCC 15442 Staphylococcus aureus ATCC 6538 DVG 8582 ATCC 14153

Antibacterial activity was determined according to EST (DD177: 1988) and performed under soil conditions with 0.03 wt. bovine serum albumen (BSA) at 19.5 ° C. The overall degree of viability was determined after 5 minutes and 30 minutes of contact using the solutions listed below and water of average hardness for control. A reduction compared to water was noted. Survived organisms were determined by culturing on nutrient tryptone-soy agar for 48 hours at 37 ° C. Decimal reductions were calculated from the survival rate. Table 1 shows the results after 5 and 30 minutes contact time.

Concentrations in the sample which represented the concentrations in the toilet bowl after use of the product of the invention were as follows:

% Amidosulfonic acid: 0.08 wt.

Hydrogen peroxide: 0.10 wt.

Amine ethoxylate: 0.06 wt. Ethomeen S / 12

Table 1 (mortality rate)

Suspension test results showing the average mortality rate, cfu / ml.

CK = total mortality

NSK = no significant mortality

Organism S. aureus E. faecium P.mirabilis P. aeruginosa land 0.03% BSA 0.03% BSA 0.03% BSA 0.03% BSA Contact time (in minutes) 5 30 5 30 5 30 5 30 acid sulfamic 0.99 NSK 2.00 0.00 NSK 0.05 1.95 NSK 0.96 NSK 2.45 0.00 NSK acid sulfamic + peroxide 1.62 NSK 2.15 0.00 NSK 0.14 1.74 NSK 0.93 NSK 2.36 1.64 NSK acid sulfamic + peroxide + amine ethoxylate 3.54 3.99 1.01 NSK 5.01 4.3 4.85 6.95 4.36 CK acid sulfamic + amine ethoxylate 3.29 3.91 1.56 NSK 5.01 2.69 4.85 6.95 4.36 CK

Initial results: Staphylococcus aureus ATCC 6538 6.99 Enterococcus faecium DVG 8582 6.99 Pseudomonas aeruginosa ATCC 15442 4.36 Proeteus mirablis ATCC 14153 4.95

A 49 ml TWEEN (TM) peptone was used as neutralizing agent. Therefore, where there is no result, <50 cfu / ml or log 50 corresponds to 1.70 survivors. The above table shows that the combination of amidosulfonic acid and amine ethoxylate improved bactericidal properties against this broad spectrum of bacteria compared to amidosulfonic acid alone. The results of the effects of disinfectants greater than 3 are indicated in bold in the table below.

In particular, it can be seen that the amidosulfonic acid itself (first example) has weak antibacterial properties which are not significantly improved by the presence of hydrogen peroxide (cf. the first two examples), but that both amidosulfonic acid and amine ethoxylate formulations (cf. the last two examples) have antimicrobial properties comparable to systems which additionally contain hydrogen peroxide (the last example).

Claims (9)

PATE NT CLAIMS Use of 0.01 to 15 wt. of an alkoxylated aliphatic amine of 8 to 18 carbon atoms and 1 to 8 alkoxylation units to improve the antimicrobial effects of an acidic antimicrobial composition containing from 0.01 to 15 wt. of amidosulfonic acid. Use according to claim 1, wherein the composition also comprises peroxygen sources. Use according to claim 2, wherein the peroxygen source is hydrogen peroxide. Use according to claims 1 to 3, wherein the alkoxylated aliphatic amine is an ethoxylated amine of the formula H (A) _X -N (R) - (A) _Y H where R represents an alkyl or alkenyl group having 8 to 20 carbon atoms, A is ethoxy or propoxy and x and y may be the same or different and represent an integer from 1 to 4. Use according to claim 4, wherein x and y are independently 1 or 2. Use according to claims 4 or 5, wherein R has 10 to 18 carbon atoms. 7. An acidic antimicrobial preparation comprising: a) 0.01 to 15 wt. of an alkoxylated aliphatic amine with 8 to 20 carbon atoms and 1 to 8 alkoxylation units, b) 0.01 to 15 wt. amidosulfonic acid, c) 1 to 10 wt. hydrogen peroxide. -128. The composition according to claim 7, wherein the alkoxylated aliphatic amine is an ethoxylated tertiary amine of the formula H (A) _X - N (R) - (A) _Y H wherein R represents an alkyl or alkenyl group having 8 to 20 carbon atoms, A is ethoxy or propoxy and x and y may be the same or different and represent an integer from 1 to 4. Composition according to claims 7 to 9, characterized in that the antimicrobial composition comprises: a) 1 to 10 wt. amidosulfonic acid, b) 1 to 10 wt. ethoxylated amine, c) 0 to 5 wt. a nonionic surfactant, d) 0.05 to 2 wt. anionic surfactant hydrotropic, e) 1 to 6 wt. hydrogen peroxide.